CN1036648C - Method and equipment for continuous catalyzing rectifying production of n-butyester acetate - Google Patents
Method and equipment for continuous catalyzing rectifying production of n-butyester acetate Download PDFInfo
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- CN1036648C CN1036648C CN94108405A CN94108405A CN1036648C CN 1036648 C CN1036648 C CN 1036648C CN 94108405 A CN94108405 A CN 94108405A CN 94108405 A CN94108405 A CN 94108405A CN 1036648 C CN1036648 C CN 1036648C
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Abstract
The present invention relates to a preparation method and equipment of n-butyl acetate. The method is characterized in that acetic acid and normal butanol are filled in a reaction rectification tower for primary reaction rectification to obtain 95 to 98% n-butyl acetate. The equipment comprises the reaction rectification tower with a pipe bundle condenser and two sections of solid acid catalysis filler layers, a reboiler, a condensing cooler, a phase separator, etc. Compared with the production capacity of the traditional sulfuric acid method, the production capability of the method of the present invention is enhanced by more than two times, the conversion rate of the acetic acid is increased, the use amount of heating steam is decreased, and the equipment corrosion is lightened.
Description
The present invention relates to a kind of production method of n-butyl acetate, particularly adopt the method and apparatus of continuous catalytic reaction rectifying production of n-butyester acetate.
N-butyl acetate is the basic Organic Chemicals of chemical industry, and it is widely used in coating, spices, organic synthesis intermediate and as the solvent of multiple organic compound.The production method of existing n-butyl acetate uses sulfuric acid to make catalyzer mostly, adopts periodical operation production, and the shortcoming of this method is: one, owing to adopt periodical operation, the generation ability of equipment is low; Two, make the catalyzer severe corrosion equipment with sulfuric acid, separating catalyst needs with the alkali neutralization from product, and catalyzer can not be reused; Three, sulfuric acid has stronger oxidisability, and the production process side reaction is many.In order to overcome the shortcoming of sulfuric acid process, the someone has studied the method for utilizing solid acid to make the Catalyst Production N-BUTYL ACETATE in recent years, disclose with Glacial acetic acid, butanols and 732 resins and D72 resin liquid phase catalytic reaction as " daily chemical industry " 89 years the 2nd phases and to have produced N-BUTYL ACETATE, but this method reaction and rectifying are not carried out in same equipment, and when reaction butanols need excessive more, cause reaction back butanols separation difficulty, and be partially soluble in and emit in the water and cause waste.
The purpose of this invention is to provide a kind of is catalyzer with the solid acid, make acetic acid and propyl carbinol obtain the method and apparatus of n-butyl acetate in a tower internal reaction and rectifying, it not only can overcome the corrosion that sulfuric acid causes equipment, reduce side reaction, and improved the throughput and the work-ing life that has prolonged catalyzer of equipment.
The present invention is achieved in that solid acid catalyst is made the catalytic filler of filling reaction fractionating tower, raw material acetic acid and propyl carbinol add from the middle and upper part opening for feed of tower, react on one side at the catalyst filling layer, distillation on one side, the n-butyl acetate product that reaction generates is discharged at the bottom of tower, its product content is 95-98.5%, and unreacted material is from the cat head phase-splitting retrieval system again of coming out.Specific embodiment is: acetic acid and propyl carbinol measure with 1: 0.9～1: 1.5 volume flow ratio, mixed in 0.4: 1～2: 1 by organic phase and raw material volume flow ratio with the organic phase of coming out from phase splitter, enter the feed zone of reaction fractionating tower through preheating, most of raw material reacts at second section catalytic filler layer, n-butyl acetate goes out from tower bottom flow, the raw material of small part gasification reacts at first section catalytic filler layer, through the pipe bundle condenser condensation, water and positive butyl ester of little acetic acid and acetic acid that reaction generates, come out from cat head in propyl carbinol backflow part back, phase-splitting after the condensate cooler cooling, moisture content is drained, and organic phase and raw material mix after the reaction fractionating tower reaction is sent in preheating back to.
The equipment that adopts according to aforesaid method has the reaction fractionating tower of two-stage catalytic packing layer, and there are condensate cooler, phase splitter, feed heater and header tank mixing tank etc. in the reaction fractionating tower top.
Below be reaction process flow process and equipment
Chemical reaction of the present invention is reversible reaction, need react under acid catalysis:
Present most of factory adopts the sulfuric acid catalysis reaction, equipment corrosion is very serious, screen through the inventor, the solid acid of selecting is preferably the polystyrene big powers acid type Zeo-karb more than 110 ℃, the transformation efficiency of its Dichlorodiphenyl Acetate can reach more than 92%, before putting into tower, catalyzer must be placed on stainless (steel) wire or the glasscloth, be rolled into right cylinder or some volume small columns with the identical size of tower diameter, be divided in two sections towers of packing into, between the shell-and tube condenser that first section is placed on material inlet section and cat head, second section is placed on below the material inlet section.
Major equipment of the present invention is a reactive distillation column, it is a cylindrical container, the top of tower is shell-and tube condenser, its effect is that the product partial condensation that reaction obtains is got off, and its structure is that steam is walked in the pipe, and water coolant is walked between pipe, the shell-and tube condenser below is first section catalytic filler layer, being feed zone then, is second section catalytic filler layer (second section catalytic filler layer also can be divided into two layers or three layers) below the feed zone, and products export pipe and reboiler inlet tube are housed at the bottom of the tower.
Auxiliary facility has condensate cooler, phase splitter, feed heater, reboiler and header tank mixing tank, wherein the tower top outlet pipe leads to condensate cooler (its effect is that water and the positive butyl ester condensation of little acetic acid that unreacted butanols, acetic acid and reaction generate are cooled down), the outlet of condensate cooler is a phase splitter, the bottom of phase splitter is the water outlet, the upper strata is the organic phase outlet, and the organic phase outlet is returned the tower opening for feed after metering and raw material mixing and preheating.
The difference part of equipment of the present invention and existing rectifying device is that tower top outlet does not flow in the tower immediately, and is mixed in the tower with raw material after first condensation cooling and the phase-splitting.
The decision of processing condition:
According to the reaction system, look into " chemical handbook, the boiling point of each material is as follows:
Water: 100 ℃
Acetic acid: 118 ℃
Propyl carbinol: 117.7 ℃
Acetic acid propyl carbinol: 126.3 ℃
So we select the opening for feed temperature of charge is 103-115 ℃, cat head pipe bundle condenser temperature out is 90-110 ℃, and the bottom product temperature out is 120-130 ℃, and condensate cooler outlet material temperature is 20-60 ℃.
The solid acid catalysis packing layer amount of filling out is calculated according to output, but first section and second section filling ratio are 1: 2.5～1: 6.
The volumetric flow rate of organic phase and raw material is 0.4: 1～2: 1, and the mol ratio of acetic acid and propyl carbinol is 1: 0.9～1: 1.5.
The present invention compares with existing sulfuric acid catalysis method, and throughput can improve more than the twice, and acetic acid conversion can improve 1%-3%, and heating steam can reduce 10%-30%, and medium greatly alleviates the corrosion of equipment.
Below in conjunction with accompanying drawing technical process of the present invention and device structure are described:
Among the figure, raw material acetic acid and propyl carbinol at header tank 1 after metering with after organic liquid such as butanols, acetic acid of coming out in the outlet pipe 14 of phase splitter 12 mixes, enter the feed zone 3 of reaction fractionating tower 4 through preheater 2, material is in the process that flows to 5 reaction of second section catalyst filling layer, the high temperature organic steam that is come out by tower bottom reboiler 7 heats, lower boiling acetic acid, butanols and water vapor, in two sections catalytic fillers 5 and 8, continue reaction, from pipeline 6, discharge the n-butyl acetate of generation flows to tower under the condensation in pipe bundle condenser 9 at the bottom of; Water and unreacted acetic acid, butanols and a spot of n-butyl acetate, then enter condensate cooler 11 from cat head pipeline 10, be chilled to below 60 ℃, come out to enter phase splitter 12 then from the bottom, the proportion of water is discharged from phase splitter bottom pipe 13 more greatly, the little discharge from top of organism proportion mixed by the raw material of pipeline 14 with header tank 1, enters reaction fractionating tower feed zone 3 then by preheater 2.
Embodiments of the invention:
Embodiment one, the reaction fractionating tower diameter is 0.3 meter, 5 meters of height overalls, wherein feed zone is 0.5 meter, 0.5 meter on first section catalytic filler layer, 3 meters on second section catalytic filler layer, catalyzer adopts the polystyrene big powers weak acid cation exchange resin of heatproof more than 110 ℃, the right cylinder made from stainless (steel) wire is contained in the tower, the mol ratio of acetic acid and positive butyl ester was by 1: 1.2, and phase splitter outlet organic phase and raw material volume flow ratio are 0.8: 1, enter in the tower by preheater 2, column bottom temperature keeps 120-130 ℃, the feed zone temperature keeps 100-110 ℃, and the shell-and tube condenser temperature out is 90-110 ℃, and the n-butyl acetate content that reaction obtains is 96-97%.
0.4 meter of embodiment two, reaction tower diameter, 6.5 meters of tower heights, 1 meter on first section catalytic filler layer, 4 meters on second section catalytic filler layer, catalyzer is identical with embodiment one, acetic acid was pressed 1: 1.0 with the ratio of positive butyl ester in the header tank, the volume flow ratio of organic phase and raw material is 1: 1, and column bottom temperature is 120-130 ℃, and the feed zone temperature keeps 103-115 ℃, shell-and tube condenser 9 temperature outs are 90-110 ℃, and the n-butyl acetate content that reaction obtains is 95-97%.
Claims (5)
1. the production method of a n-butyl acetate, be under the solid acid catalyst effect, acetic acid and propyl carbinol liquid-phase catalysis generate n-butyl acetate, it is characterized in that: acetic acid and the propyl carbinol form with successive reaction rectifying in reaction fractionating tower (4) is carried out, n-butyl acetate flows out from the reactive distillation tower bottom, unreacted organic phase comes out to mix retrieval system with raw material after phase splitter (12) separates moisture content from cat head, specific embodiment is acetic acid and propyl carbinol with 1: 0.9～1: 1.5 volume flow ratio metering, mixed in 0.4: 1～2.0: 1.0 by organic phase and raw material volume flow ratio with the organic phase of coming out from phase splitter (12), enter the feed zone (3) of reaction fractionating tower through preheating, most of raw material reacts at second section catalytic filler layer (5), n-butyl acetate goes out from tower bottom flow, the raw material of small part gasification reacts at first section catalytic filler layer (8), through pipe bundle condenser (9) condensation, water and positive butyl ester of little acetic acid and acetic acid that reaction generates, come out from cat head in propyl carbinol backflow part back, phase-splitting after condensate cooler (11) cooling, moisture content is drained, and sends the reaction fractionating tower reaction after organic phase and raw material mix back to.
2. method according to claim 1, the vapor phase exit temperature that it is characterized in that pipe bundle condenser (9) is 90-110 ℃, the temperature of reaction fractionating tower (4) bottom discharge is 120 ℃-130 ℃.
3. method according to claim 1 is characterized in that solid acid catalyst is the polystyrene big powers acid-type ion-exchange resin of heatproof more than 110 ℃.
4. the described method required equipment of claim 1, it is characterized in that reaction fractionating tower (4) comprises shell-and tube condenser (9), first section catalytic filler layer (8), feed zone (3) and the second section catalytic filler layer (5) below condenser (9) that is contained in the tower upper end, first section and second section catalyst loading ratio are 1: 2.5～1: 6, reaction fractionating tower (4) top is connected to condensate cooler (11), condensate cooler (11) outlet connects phase splitter (12), phase splitter (12) is received between header tank (1) and the preheater (2), links to each other with reboiler (7) at the bottom of the tower.
5. equipment according to claim 4 is characterized in that the right cylinder that make for stainless (steel) wire or glass fiber mesh catalytic filler layer (8) and (5), the inside solid acid catalyst of packing into.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94108405A CN1036648C (en) | 1994-07-16 | 1994-07-16 | Method and equipment for continuous catalyzing rectifying production of n-butyester acetate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94108405A CN1036648C (en) | 1994-07-16 | 1994-07-16 | Method and equipment for continuous catalyzing rectifying production of n-butyester acetate |
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| Publication Number | Publication Date |
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| CN1107136A CN1107136A (en) | 1995-08-23 |
| CN1036648C true CN1036648C (en) | 1997-12-10 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN94108405A Expired - Fee Related CN1036648C (en) | 1994-07-16 | 1994-07-16 | Method and equipment for continuous catalyzing rectifying production of n-butyester acetate |
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| CN (1) | CN1036648C (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085653C (en) * | 1997-11-25 | 2002-05-29 | 河南省科学院化学研究所 | Continuous butyl acetate producing process |
| KR100563596B1 (en) | 1998-03-25 | 2006-03-22 | 술저 켐테크 악티엔게젤샤프트 | Process and apparatus for the production of butylacetate and isobutylacetate |
| CN100371062C (en) * | 2005-09-16 | 2008-02-27 | 上海应用技术学院 | Novel catalytic reaction and separation device |
| CN100402485C (en) * | 2006-04-19 | 2008-07-16 | 广西壮族自治区化工研究院 | Method for reaction rectification coupling continuous preparation of and series acetate |
| CN101481296B (en) * | 2008-01-11 | 2013-05-01 | 山东科技大学 | Production process for preparing sec-butyl alcohol by mixed C4 reaction distillation method |
| CN101219950B (en) * | 2008-01-25 | 2010-06-16 | 天津大学 | System and method for producing n-butyl acetate by using methyl acetate and n-butyl alcohol ester exchange reaction |
| CN102294204B (en) * | 2011-07-07 | 2013-07-10 | 南京大学 | Integrated system technology of fixed bed and injection floating bed coupled with separating unit |
| CN102491900A (en) * | 2011-12-08 | 2012-06-13 | 厦门大学 | Method for preparing diethylene glycol dibenzoate |
| CN102690197A (en) * | 2012-05-29 | 2012-09-26 | 江门谦信化工发展有限公司 | Method for preparing acetic acid mixed butyl ester by continuous reaction and rectification |
| CN103467285B (en) * | 2013-06-09 | 2015-03-25 | 百川化工(如皋)有限公司 | Method for reducing acidity of acetate |
| CN104592027A (en) * | 2015-02-13 | 2015-05-06 | 厦门大学 | Method for preparing methyl benzoate |
| CN104860819B (en) * | 2015-05-21 | 2017-06-16 | 中建安装工程有限公司 | Transformation and heat pump distillation integrated separation butyl acetate and the method and system of n-butanol |
| CN109851484B (en) * | 2017-11-30 | 2020-11-27 | 中国科学院大连化学物理研究所 | Catalytic rectification device and method for preparing methylal from methanol and formaldehyde |
| CN109701470B (en) * | 2019-02-19 | 2021-03-02 | 蔚林新材料科技股份有限公司 | Tower type micro reaction device for continuously synthesizing 2-mercaptobenzothiazole |
| CN113070007A (en) * | 2021-03-01 | 2021-07-06 | 南京诺奥新材料有限公司 | Synthesis device and synthesis method of propyl propionate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1143740A1 (en) * | 1983-06-17 | 1985-03-07 | Центральный научно-исследовательский и проектный институт лесохимической промышленности | Method of obtaining butylacetate |
| EP0483826A2 (en) * | 1990-10-31 | 1992-05-06 | Nippon Petrochemicals Company, Limited | Method for producing lower alkyl acetate |
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1994
- 1994-07-16 CN CN94108405A patent/CN1036648C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1143740A1 (en) * | 1983-06-17 | 1985-03-07 | Центральный научно-исследовательский и проектный институт лесохимической промышленности | Method of obtaining butylacetate |
| EP0483826A2 (en) * | 1990-10-31 | 1992-05-06 | Nippon Petrochemicals Company, Limited | Method for producing lower alkyl acetate |
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| CN1107136A (en) | 1995-08-23 |
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